Herbicidal nu-surstituted arylimides



United States Patent 3,158,650 PEREECEEAL N-SUESTETUTEE) ARYLRQHDESEdward David Weii, Lewiston, and Jerome Linder, Niagarn Felts, N.Y.,assignors to Hooker Qhernical (Zorporation, Niagara Falls, N.Y., acorporation of New York No Drawing. Filed May 25, 1% Ser. No. 112,528

(Ci. 26tl-562 (Jlaims.

This invention describes new and useful imide compositions of matterwhich have valuable herbicidal properties.

More particularly, this invention relates to novel N- substitutedarylimides having phytotoxicity against various broadleaf weeds andannual grass. These compositions have the structure:

wherein R is a saturated or unsaturated alpha methyl substitutedaliphatic radical of from two to five carbon atoms having at least onemethyl group on the alphacarbon atom, and R is chosen from the groupconsisting of hydrogen and saturated or unsaturated aliphatic radicalsof from one to three carbon atoms, and R is a chlorinated aryl radicalchosen from the group consisting of 3,4-dichlorophenyl and3-chloro-4-methylphenyl. The compounds of the invention are colorlessoils or lowmelting solids.

Representative examples of the compounds of this invention areN-formyl-N-propionyl-3 ,4-dichloroaniline, N-formyl-N-isobutyryl-3,4-dichloro aniline, N-formyl-N-methacrylyl-3 ,4-dichloro aniline,N-acetyl-N-propionyl-3 ,4-dichloro aniline, N-acetylN-propionyl-3-chloro-4-methylaniline, N-acetyl-N-propionyl-3,4-dichloroaniline, N- 3,4-dichlorophenyl propionimide, N- 3-chloro-4-methylphenyl)propionimide, N- 3 ,4-dichlorophenyl isobutyrimide, N-3-chloro-4-methylphenyl) isobutyrimide, N- (3 ,4-dichlorophenylmethacrylimide, N- (3-chloro-4-methylphenyl) methacrylimide,N-acetyl-N-methacrylyl-3,4-dichloroaniline,N-acetyl-N-methacrylyl-3-chloro-4-rnethylaniline, N-acetyl-(Z-methylpentanoyl -3 ,4-dichloro aniline, N-acetyl-N-(Z-methylpentanoyl) -3-chloro-4- methylaniline, N-3,4-dichlorophenyl-2-methylbutyrimide, N- 3-chloro-4-methylphenyl-2-methylbutyrimide, N-acetyl-N- (Z-methylbutyryl) -3,4-dichloroaniline, N -acetyl-N- (Z-methylbutyryl)-3-chloro-4-methylaniline, N-n-butyryl-N-propionyl-3,4-dichloroaniline,N-n-butyryl-N-propionyl-3-chloro-4-methylaniline,N-n-butyryl-N-isobutyryl-3 ,4-dichloro aniline, N-n-butyryl-N-isobutyryl-3 -chloro-4-methylaniline, N-n-butyryl-N-methacrylyl-3 ,4-dichloro aniline, N-n-butyryl-N-methylacrylyl-3-chloro-4-methyl aniline,N-n-butyryl-N-Z-methylpentanoyl-3 ,4-dichloro aniline,N-n-butyryl-N-Z-methylp entanoyl-3 -chloro-4- methylaniline,N-caproyl-N-propionyl-3 ,4-dichloroaniline, N-caproyl-N-isobutyryl-3,4-dichloroaniline, N-caproyl-N-methacrylyl-3 ,4-dichloro aniline,N-crotonyl-N-propionyl-3 ,4-dichloroaniline, N-crotonyl-N-isobutyryl-3,4-dichloroaniline,

3,158,65fi Patented Nov. ,24, 1964N-crotonyl-N-methacrylyl-3,4-dichloroaniline,N-Z-ethylhexoyl-N-propionyl-3,4-dichloroaniline,N-2-ethylhexoyl-N-isobutyryl-3,4-dichloroaniline, N-Z-ethylhexoyl-N-methacry1yl-3,4-dichloroaniline,N-capryl-N-propionyl-3,4-dichloroaniline, VN-capryl-N-isobutyryl-3,4-dichloroaniline,N-capryl-N-methacrylyl-3,4-dichloroaniline,N-caprylyl-N-propionyl-3,4-dichloroaniline,N-caprylyl-N-isobutyryl-3,4-dichloroaniline, N-oaprylyl-N-methacrylyl-3,4-dichloroaniline,N-caprylyl-N-Z-methylpentanoyl-3-chloro-4 methylaniline.

The preferred species are those in which R is acetyl or n-butyryl, forreasons of cost in relation to activity.

The novel compounds of this invention are especially advantageouscompared to many herbicides of the prior art (for example 2,4-D), inthat they are substantially non-injurious to commercially valuable cropsand turf grasses at rates of application (about one-half to ten poundsper acre), Where they exert a pronounced phytotoxic effect againstbroadleaf perennial weeds and annual gasses. Examples of commerciallyimportant crops on which these novel imide compositions may bebeneficially used without consequential injury to the crops are amongother, rice, corn, carrots, potatoes, tobacco, pineapple, cotton, aswell as the aforementioned desirable perennial turf grasses.

The method of the invention comprises spraying the compounds of theinvention, most conveniently as an emulsion in water by the aid of anorganic solvent and emulsifier, onto the weed seedlings to be killed.Rates of one-half to ten pounds of toxicant per acre are preierred, theexact rates preferable in any given situation depending on weedsspecies, stage of growth, vigor degree of kill required, and otherfactors which will be obvious to those skilled in the art.

The compounds of the invention may be employed in combination with otherherbicides and with fungicides, insecticides, growth stimulants, andfertilizers if desired. Their action may be enhanced by suitable choiceof solvents, wetting agents, penetrating agents, Spreaders,

stickers and synergists. The use of the commercial spray additives knowncollectively as spreader-stickers is particularly to be recommended withthese compounds.

The novel imides of this invention are generally made by heatingstoichiometric amounts of the appropriately substituted acid chlorideand the anilide or aniline until the proper number of molar equivalentsof hydrogen chloride is evolved. For example, where R and R are the samethe compounds are conveniently made by the prolonged heating of R NHwith two moles of R COCl until two molar equivalents of hydrogenchloride are evolved. In those instances where R and R are different,the novel products are made by the extended heating of R COCl with RCO'NHR or R COCl with l R CONHR until one molar equivalent of hydrogenchlofrared and ultraviolet spectra.

or a chlorohydrocarbon or nitroai'omatic solvent may be expeditiouslyused. The reaction is operable at temperatures ranging from seventy totwo hundred and fifty d grees, although the most favorable temperaturesappear 4 Example 2.N-Acetyl-N-Propionyl-3,4-Diclzloroaniline A solutionconsisting of one hundred and two parts of 3,4-dichloroacetanilide,sixty-five parts of propionyl chloride and live hundred parts of curneneis heated to reflux to be from one hundred to two hundred degrees centiuntil 18.2 parts of gaseous hydrochloric acid evolves. gradi Obviouslythe reactlon being fmjctlon i The curnene is distilled off leaving anOil which on crystal- 1: 4-D 1 i reaciams and gf i Gimp-0t bcbstfhwdwith i lization from hexane gives a white solid melting at sixty sion,buu the extreme .imilts tot time are etween onewour to sixqhfive degreescentigrade if savenly'two e f l f f toflgetefn Analysis.Calcd. for c Hci No (:1, 27.3 percent; ours being a more 511a E Ben/t f'i N, 5.3percent. Found: Cl 27.6 percent; N, 4.5 percent. atures are used, thereaction time under given conditions, will approach the longer reactiontimes, while at higher Examples temperatures, the converse will usuallybe true. An HCl Using thg Same techniques and equipment the f ll w.

a we acceptor S as py f f 1S Often lloellll 111 accfileralmg ingexamples show representative products that are prethe reaction aI 1dParmimng lower FQ temP eT3tuY6S, l5 pared from the reactants asindicated. Physical characterbut not essentlal l0 Operable coildltlofisand satlsfactory istics and elemental analysis established the formationof y j P P FP and use of F1656 nova the desired products in each case.Included in the follow- COIIIPQSIUODS are glveil fl pl whlqh {CHOW inglist are some compounds related to, but not included These furthefe{iampl?s 06mg merely illustrative i in, the class of compounds of theinvention. These are workings of this invention, are not to be construedas limitincluded f comparison purposes s Table I in the s ecification orclaims in an manner whatsoever.

g p c y L Herbzczdal ACllVll'y of Compounds of Examples 1-18 Exam le1.-N- 3,4-Dichl0r0 hen 1 r0 ionimide p p 3 p p The compounds weredissolved in a mixture of 1:1 A solution consisting of 32.4 parts of3,4-dichloroxylene-isophorone and emulsified in water with the helpaniline, forty-seven parts of propionyl chloride and four 2 of acommercial polyoxyethylene sorbitan laurate-alkylhundred parts of cumeneis heated at reflux until l4.6 aryl sulfonate emulsifier. They aresprayed at four parts of gaseous hydrochloric acid evolves. The curnenepounds of herbicide per acre on a mixed population of is distilled offletving an oil which on crystallization from seedlings of broadleafweeds (principally lambsquarters, hexane gives thirty-five parts of awhite solid melting at pigweed, ragweed, and mustard), and a mixedpopulation sixty-eight to seventy degrees centigrade. 3.0 of grassyweeds, (principally crabgrass, barnyard grass, AizaIysis.-Calcd. for C HCl NO Cl, 25.9 percent; cheatgrass and millet). After one week, theellect of N, 5.1 percent. Found: Cl, 25.1 percent; N, 4.6 percent. theherbicides was evaluated. See Table ll.

Table I CompoundNo. R1 R2 R3 M.P., 0. C1 Calcd. 01 Found N Galcd. NFound 1 -C2H5 O2H5 3,4-dichloronheny1 68-70 25.9 25.1 5.1 4.6

2 CZH OH3 -5 27.3 27.6 5.3 4.5

3 GH(OH3); CH(CHa)z -6 23.5 23.5 4.6 3.9

4 OH;, OH; 78-80 28.8 29.1 5.7 5.8

5 nGiH7 nCaH7 Oil 23.5 23.3 4.6 4.1

([JHa (13 s 6 G=OH2 -G=CH2 Oil 23.8 23.1 4.7 4.2

/CH3 CH3 7 --OH C Oil 19.9 19.2 3.93 3.4

C3H7 02111 e s C=CH2 GE; .do Oil 26.1 25.9 5.15 5.0

/CE 9 CH CH;; d0 Oil 23.5 23.2 4.64 4.25

10 C2H C2H5 4-ehlorophenyl 45-65 14.6 14.6 5.85 5. 32

11 -O H -CzH5 s-clilorophenyl 41-2 14.0 14.2 5.85 5.51

12 O H -O2H 3-chloio-4-methylphenyl 367 14.0 14.2 5.60 5.50

/CH3 13 -05 CH3 do Oil 14.2 14.0 5.85 5.43

14 0H5 OH d0 Oil 14.8 14.2 5.85 5.30

(1113 15 O=0Hi OH3 do Oil 12.6 12.1 4.99 4.30

w 16 -o=o11, O3H 3,4-dichlorophenyl Oil 25.5 23.8 4. 66 4.95

17 -CzH I1C3H7 dO Oil 24.6 24.2 4.86 4.30

is C H 11-0111; do Oil- 20.7 20.2 4.07 3.90

Table II Action on Action on Cpd. N0. Broadleaf Grassy Species Species AA A 13+ A A O G O C A A 13+ 13-]- A A 13+ B O C C O B B 18+ 13+ A A A BA A A A 13+ B Scale:

A='70100% kill (satisfactory control). B:3070% kill (fair control).C=3(l% kill (essentially no control).

The compounds one to eighteen were sprayed on one-month old stands offield corn, carrots, potatoes, and rice at four pounds per acre. Afterone week inspection of these crops indicated no substantial injury,Whereas Weed seedlings of ragweed, p'igweed, foxtail and cheatgrasspresent at the time of spraying were killed.

We claim: 1. An N-substituted arylimide having the structure wherein Ris a monovalent radical selected from the group consisting of alkyl andalkenyl of two to five carbon atoms, said radical being branched With amethyl group at the alpha carbon thereof when it is of three to fivecarbon atoms, R is selected from the group consisting of hydrogen, alkyland alkenyl of from one to nine carbon atoms, and R is selected from thegroup consisting of 3'-chloro-4-rnethylphenyl and 3,4-dich1orophenyl.

. N-acetyl-N-propionyl-3,4-dichloroaniline.

. N-n-butyryl-N-propionyl-3,4-dichloroaniline.

4. N-acetyl-N-isobutyryl-S,4-dichloroaniline.

5. N-n-butyryl-N-isobutyryl-3,4-dichloroaniline.

6. N-acetyl-N-methacrylyl-3,4-dichloroaniline.

7. N-n-butyryl-N-rnethacrylyl-3,4-dichloroaniline.

DAN

. N-(3,4-dichlorophenyl)propionimide.N-(3,4-dichlorophenyl)isobutyrimide. O.N-(3,4-dichlorophenyl)methacrylimide.

References Cited in the file of this patent UNITED STATES PATENTS2,226,672 Smith Dec. 31, 1949 2,648,621 Gerjovich et al Aug. 11, 19532,929,844 Surrey Mar. 22, 1960 2,977,212 Tischler Mar. 28, 19612,983,755 Kollonitsch et a1. May 9, 1961 2,992,091 Harmon et al. July11, 1961 FOREIGN PATENTS 1,039,779 Germany Sept. 25, 1958 OTHERREFERENCES Gertler et al.: U.S. Dept. of Agriculture, AgricultureResearch Svc., ARS-33-14, pp. 1-12, pp. 4, 5 and 10 relied on (1955).

1. AN N-SUBSTITUTED ARYLIMIDE HAVING THE STRUCTURE